JPS62169681A - Recording material - Google Patents

Abstract

PURPOSE:To enhance a color forming property, raw preservability and the stability of a developed color image, by having a salicylic acid derivative having an aryloxy group and an alkyloxy group as substituents or a metal salt thereof contained as an electron receptive compound. CONSTITUTION:In a recording material containing an electron donating leuco dye and an electron receptive compound, a salicylic acid derivative having an aryloxy group and an alkyloxy group as substituents or a metal salt salt thereof is contained as the electron receptive compound. The pref. salicylic acid derivative is represented by formula (wherein Ar is an aryl group, X is a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, M is a n-valent metal atom and m and an are an integer). When the leuco dye and the electron receptive compound are adapted to the recording material, thereby are used in the form of a microdispersion or a minute droplet. Because the use amounts of the electron donating leuco dye and the electron receptive compound are set according to a desired coating thickness, the form of pressure- sensitive copy paper, a capsule preparing method and other conditions, they may be appropriately selected corresponding to said conditions.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of the Invention) The present invention relates to a recording material, and in particular to a recording material using an electron-donating colorless dye and an electron-accepting compound that have improved color development, shelf life, and stability of colored images. related to recorded materials.

(Prior Art) Recording materials using an electron-donating colorless dye and an electron-accepting compound are already well known as pressure-sensitive paper, heat-sensitive paper, light-sensitive pressure-sensitive paper, electrically conductive heat-sensitive recording paper, and the like.

For example, British patent, 2/≠07≠ri, US patent≠1ro
oza, $443J Octopus O1 Special Public Sho-λ3, Ri,
22, Tokukai Akira! 7-/7ri, ♂36, 60-113,
3j&, direction 60-/23. j! Familiar with t7 etc.

The performance that a recording material should have is (11) sufficient color density and color development sensitivity, (2) no fogging, (3) sufficient fastness of the color material after color development, (
4) Appropriate color hue and suitability for copying machines (5) S
/N ratio should be high, and (6) the color former should have sufficient chemical resistance, but currently there is no trout that completely satisfies these requirements.

In particular, the development of heat-sensitive recording materials has been remarkable in recent years, but heat-sensitive recording materials have the disadvantage that capri is caused by solvents and the like, and the color formers are subject to discoloration and fading due to oils, fats, chemicals, and the like. Therefore, stationery and office supplies such as water-based ink pens, oil-based ink pens, fluorescent ink pens, ink ink, adhesives, glue, diazo developer, hand cream, etc.
The inventors of the present invention discovered that an electron-donating colorless dye and an electron-accepting compound, which caused the white part to develop color or the colored part to discolor and fade when it came into contact with cosmetics such as emulsions, significantly diminishing the commercial value. For each, its oil solubility, water solubility,
We have pursued the development of good materials for recording materials and recording materials by focusing on characteristics such as distribution coefficient, pKa polarity of substituents, position of substituents, and changes in crystalline solubility when mixed.

(Object of the Invention) Therefore, the object of the present invention is to provide a recording material using a material that has good color development properties, shelf life, and stability of color development image quality, and also satisfies other necessary conditions.

(Structure of the Invention) The object of the present invention has been achieved by a recording material characterized in that it contains a salicylic acid derivative or a metal salt thereof having an aryoxy or alkyloxy group as a substituent as an electron-accepting compound. .

Among the salicylic acid derivatives according to the present invention, those represented by the following general formula are preferred.

In the above formula, Aru represents an aryl group, X represents a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, M represents an n-valent metal atom, and m and n represent integers.

Note that the alkyl group represents a saturated or unsaturated alkyl group or a cyclonalkyl group, which has a substituent such as an aryl group, an alkoxy group, an aryloxy group, a halogen atom, an acylamino group, an aminocarbonyl group, or a cyano group. Also, the aryl group represents a phenyl group, a naphthyl group, or a heteroaromatic group, and these include an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a nitro group, a cyan group, a substituted carbamoyl group. , a substituted sulfamoyl group, a substituted amino group, a substituted oxycarbonyl group, a substituted oxysulfonyl group, a thioalkoxy group, an arylsulfonyl group, or a phenyl group.

Among the substituents represented by Ar in the above formula, aryl groups having 6 to 2 carbon atoms are preferable, and among the substituents represented by X, hydrogen atoms, alkyl groups having 1 to 2 carbon atoms, carbon atoms/ The alkoxy group, chlorine atom, and fluorine atom of -1 are preferable, and among the metal atoms represented by M, zinc, aluminum, magnesium, and calcium are preferable, and an integer of mFi/ to 10 is preferable.

Among the substituents of the aryl group represented by Ar, alkyl groups having 1 to 2 carbon atoms, aralkyl groups having 7 to 16 carbon atoms, alkoxy groups having 1 to 1 carbon atoms, halogen atoms, phenyl groups, etc. 7IC haalkoxycarbonyl group is preferred.

Preferred examples of the aryl group represented by Ar include Te Co., phenyl group, tolyl group, ethylphenyl group, propylphenyl group, butylphenyl group, cyclohexylphenyl group, octylphenyl group, nonylphenyl group, dodecylphenyl group, benzylphenyl group , phenethyl phenyl group, cumylphenyl group, xylyl group, diphenethylphenyl group, methoxyphenyl group, ethoxyphenyl group, benzyloxyphenyl group, octyloxyphenyl group, dotesyloxyphenyl group, chlorophenyl group, fluorophenyl group, phenylphenyl group group, hexyloxycarbonylphenyl group, benzyloxycarbonylphenyl group, dodecyloxycarbonylphenyl group, naphthyl group,
Examples include methylnaphthyl group and chloronaphthyl group.

OR group ofl substitution RuCo O(H or tiM"/'n
) The ortho, meta or para position relative to the group is preferred, and the para position is particularly preferred.

From the viewpoint of water insolubility, the salicylic acid derivative according to the present invention preferably has a total number of carbon atoms of 72 or more, particularly preferably 72 or more carbon atoms.

The recording material using the salicylic acid derivative according to the present invention is
The color density is sufficient, and the developed pigment is extremely stable.
It is particularly advantageous in terms of long-term preservation of records, as it hardly causes discoloration or fading even after long-term light irradiation, heating, or humidification. In addition, when used in heat-sensitive recording materials, there is no drawback that uncolored areas develop color due to solvents, etc., or the colored body discolors or fades due to oils, fats, chemicals, etc., making it ideal as an electron-accepting compound for recording materials. It has similar performance.

A- Next, specific examples of the electron-accepting compound according to the present invention will be shown.

Hiro-β-phenoxyethoxysalicylic acid, ti-(Hiro-phenoxybutoxy) salicylic acid, ≠-(t-phenoxyhexyloxy) salicylic acid, ≠-(j-phenoxyamyloxy) salicylic acid, p-(lr-phenoxyoctyloxy) Salicylic acid, Hiro-(10-phenoxydecyloxy) salicylic acid, φ-β-p-)lyloxyethoxysalicylic acid, Hiro-β-m-)lyloxyethoxysalicylic acid, Hiro-β-0-)lyloxyethoxysalicylic acid, Gu β-p-ethylphenoxyethoxysalicylic acid, ≠-β-p-isopropylphenoxyethoxysalicylic acid, ≠-β-p-t-butylphenoxyethoxysalicylic acid, Hiro-β-p-cyclohexylphenoxyethoxysalicylic acid, Gu β-pt -Octylphenoxyethoxysalicylic acid, ≠-β-p-nonylphenoxyethoxysalicylic acid, ≠-β-p-dodecylphenoxyethoxysalicylic acid, Hiro-β-p-benzylphenoxyethoxysalicylic acid, II-(,2-p-α-phenethyl phenoxyethoxy) salicylic acid, terβ-0-
Methoxyphenoxyethoxysalicylic acid, Gu β-p-
Cumyloxyethoxysalicylic acid, Hiro-β-(J, 44
-dimethylphenoxy)ethoxysalicylic acid, goo β-
(j,4A-dimethylphenoxy)ethoxysalicylic acid, ≠-β-(J,!-dimethylphenoxy)ethoxysalicylic acid, ref.-β-(λ, 4A-bis-α-phenethylphenoxy)ethoxysalicylic acid, ref.-β-p- Methoxyphenoxyethoxysalicylic acid, Gu β-p-ethoxyphenoxyethoxysalicylic acid, Gu β-p-benzyloxyphenoxyethoxysalicylic acid, ≠-β-p-
Dodecyloxyphenoxyethoxysalicylic acid, μmβ
-p-chlorophenoxyethoxysalicylic acid, β-
p-Phenylphenoxyethoxysalicylic acid, φ-β-
p-cyclohexylphenoxyethoxysalicylic acid, ≠
-β-p-benzyloxycarbonylphenoxyethoxysalicylic acid, l-β-p-dodecyloxycarbonylphenoxyethoxysalicylic acid, Cun β-7tyl (
2) Oxyethoxysalicylic acid! -β-p-ethylphenoxyethoxysalicylic acid, Hiro-β-phenoxyethoxy-6-methylsalicylic acid, ≠-β-phenoxyethoxy-6-chlorosalicylic acid, Hiro-β-phenoxyisopropyloxysalicylic acid, etc. and their zinc salts, aluminum salt, calcium salt, etc.

These may be used alone or in combination.

Further, these electron-accepting compounds can be used in combination with well-known electron-accepting compounds such as salicylic acid derivatives, phenol derivatives, phenol resins, and acid clay. Some examples of these include tert-butylphenol, ≠-phenylphenol, hydroxydiphenoxide, α-naphthol, β-naphthol, hexyl≠-hydroxybenzoate 1.2. J'-
Dihydroxybiphenyl, +21.2-bis(4!-
Hydroxyphenyl) furo/qn (bisphenyl A)
,≠,ri'-inviridenebis(2-methylphenol-yl), i,i-bis-(3-chloro-≠-hydroxyphenyl)cyclohexane, /,/-his(3-chloroda-hydroxyphenyl)-co Ethylbutane, ≠,
3′-Secondary-isooctylidene diphenol, 4
(-tert-octylphenol, French, p' -5e
c-Butylidene diphenol, <tneal-methylphenylphenol, Hiroshi.

Da'-Isopentylidene diphenol, Ri, San'-Methylcyclohexylidene diphenol, Ri.

Hiro'-dihydroxydiphenyl sulfide/.

3-his-(3'-hydroxycumyl)benzene, 7
．． 3-bis-(3-hydroxycumyl)benzene,
Da, San'-thiobis(A-1crt-butyl-3-methylphenol), ≠, San'-dihydroxydiphenyl sulfone, Hydroquinone monobenzyl ether, San-
Hydroxybenzophenone, 2.4I-dihydroxybenzophenone, polyvinylbenzylox7carbonylphenol, co-ri.

Reference'-trihydroxybenzophenone, J, J'.

4A, 4! '-tetrahydroxybenzophenone, hiro-dimethyl hydroxyphthalate, ≠-methyl hydroxybenzoate, co, ≠ III-trihydroxydiphenylsulfone, l,! -Bis-p-hydroxyphenyl is methane, l,6-bis-p-hydroxyphenoxyhexane, tolyl dihydroxybenzoate, ≠-hydroxybenzoic acid α-phenylbenzyl ester, ≠-phenylpropyl hydroxybenzoate, g-hydroxybenzoic acid H
Phenethyl, μm-p-chlorobenzyl hydroxybenzoate, p-methoxybenzyl l-hydroxybenzoate, benzyl q-hydroxybenzoate, Hirohi)
"Roxybenzoic acid-m-chlorobenzyl ester, dihydroxybenzoic acid β-7 enethyl ester, ≠-hydroxy, z I , a / -dimethyl diphenyl sulfone, β-7 enethylorselinate, cinnamyluoli Serinate, orcelJ7 acid-o-chlorophenoxyethyl ester, 0-ethylphenoxyethyl orseinate, 0-phenylphenoxyethyl orseinate, m-phenylphenoxyethyl orseinate, λ.

Hiro-dihydroxybenzoic acid-β-3'-t-butyluda'-hydroxyphenoxyethyl ester, /t
-F Ru u -p-hydroxyphenylsulfonyloxybenzene, ≠-N-benzylsulfamoylphenol, J,4A-dihydroxybenzoic acid-p-merbenzyl ester, co,F-dihydroxybenzoic acid-β-phenoxyethyl ester, co, 4cm dihydroxy-6-methylbenzoic acid benzyl ester, bis-Hiro-hydroxyphenylacetate methyl, ditolylthiourea, +, p'-diacetyldiphenylthiourea, 3-
Phenylsalicylic acid, 3-cyclohexylsalicylic acid,
3.3-di-tert-butylsalicylic acid, 3°! -didodecylsalicylic acid, 3-methyl=! -Benzyl salicyl H1! -Phenyl-! −(α.

α-dimethylbenzyl)salicylic acid, 3. ! −G (α
-methylbenzyl)salicylic acid, -monohydroxy/-
Aromatic carboxylic acids such as benzy-3-naphthoic acid, 3
．． Organic color developers such as phenolic resins such as j-dicyclopentagenylsalicylic acid, para-phenyl phenol-formalin resin, para-butylphenol-acetylene resin, and combinations of these organic color developers such as zinc magnesium, aluminum, and calcium. , salts with polyvalent metals such as titanium, manganese, tin, and nickel, and hydrohalic acids such as hydrogen chloride, hydrogen bromide, and hydrogen iodide, boric acid, silicic acid, phosphoric acid, sulfuric acid, nitric acid, and perchloric acid. Inorganic acids such as halides such as acids, aluminum, zinc, nickel, tin, titanium, boron, acid clay, activated clay, attapulgide, bentonite, colloidal silica, aluminum silicate, i-gnesium silicate, zinc silicate, tin silicate, zinc rhodan. , inorganic color developers such as zinc chloride, iron stearate, cobalt naphthenate, nickel peroxide, ammonium nitrate, aliphatic carboxylic acids such as oxalic acid, maleic acid, tartaric acid, citric acid, succinic acid, stearic acid, benzoic acid, One or more of paratertiary butylbenzoic acid, phthalic acid, gallic acid, and gallic acid are used.

The electron-donating colorless dye according to the present invention includes triphenylene 3
- Nylmethanephthalide compounds, fluoran compounds, phenothiazine compounds, indolyl 7-thalide compounds,
There are various compounds such as leucoauramine compounds, rhodamine lactam compounds, triphenylmethane compounds, triazene compounds, and spiropyran compounds.
To illustrate some of them, as a triarylmethane compound, 3゜3-bis(p-dimethylaminophenyl)
-j -dimethylamino 7-thallide (i.e. crystal violet lactone), J, J-bis(p-dimethylaminophenyl) phthalide, J-(p-dimethylaminophenyl)-J-(/, J-dimethylindole-3- yl)phthalide, 3-(p-dimethylaminophenyl)-J
-(,2-methylindol-3-yl)phthalide, etc., and diphenylmethane compounds include ≠, 4"
-bis-dimethylaminobenzhydrin benzyl ether, N-halophenyl-leucoolamine, N-x,
a.

! -trichlorophenylleucoolamine 1E4, xanthine compounds include rhodamine-/Hiro-B-anilinolactam, rhodamine (p-nitroanilino)lactam, rhodamine B (p-chloroanilino)lactam, 2-dibenzylamino-6 -diethylaminofluorane, co-anilino 6-diethylaminofluoran, co-anilino 3-methyl-6-dinithylaminofluoran, co-anilino 3-methyl-6-cyclohexylmethylaminofluorane, J-0-chloroanilino-6-diethylaminofluoran , J-m-chloroanilino-t-diethylaminofluorane, λ-(3,≠-
dichloroanilino)-t-diethylaminofluorane,
co-octylamino-6-jethylaminofluorane,
λ-Legihexylamino-6-diethylaminofluorane J-m-)lifluoromethylanilino-6-diethylaminofluorane, coptylamino-3-chloro-6-
Diethylaminofluoran, coethoxyethylamino-3-chloro-6-diethylaminofluoran, J-p
-chloroanilino-3-methyl-t-dibutylaminofluorane, coanilino 3-methyl-A -dioctylaminofluorane, coanilino 3-chloro-6-
Dinithylaminofluorane, Kodiphenyla ε No 6
-ethylaminofluorane, co-anilino-3-methyl-4-diphenylaminofluorane, co-anilino-6-diethylaminofluorane, co-anilino-3-methyl-A-N-ethyl-N-ynamylaminofluorane, -1-anilino-3 -Methyl-yoichichloro-t-diethylaminofluorane, co-anilino-3-methyl-4
-diethylamino-7-methylfluorane, -monoanilino-3-methoxy-6-cyptylaminofluorane, J
-o-chloroanilino-t-dibutylaminofluorane, col-10roanilino-3-ethoxy-A -N-
Ethyl-N-isoamylaminofluorane, co-0-chloroanilino-4-p-butylanilinofluorane, -
1-anilino 3-pentadecyl-6-diethylaminofuran, co-anilino 3-ethyl-t-dibutylaminofuran, co-anilino 3-methyl-6-diethylaminofuran, 3
'-dichlorofluorane, coo-)cyidino-3-methyl-6-diitupropylamino-C, zl-dimethylaminofluorane, 2-anilino-3-ethyl-t-
N-ethyl-N-ynamylaminofluorane, co-anilino 3-methyl-A -N-ethyl-N-r-methoxypropylaminofluorane, -monoanilino-3-chloro-A -N-ethyl-N-amyl Examples of thiazine compounds include benzoyl leucomethylene blue and p-nitrobenzoyl leucomethylene blue. Examples of spiro compounds include 3-methyl-spiro-dinaphthopyran and 3-nityl-spiro-dinaphthopyran.
Zinaftopyran! ,! '-Cyclolosespiro-dinaphthopyran, 3-benzylspiro-dinaphthopyran,
Examples include 3-methyl-naphtho-(3-methoxy-benz)spiropyran and 3-propyl-spiro-dibenzopyran.

When these colorless dyes and electron-accepting compounds are applied to recording materials, they are used in the form of fine dispersions or fine droplets.

l7- For use with pressure sensitive paper, U.S. Patent No. 2. ! Oj,≠7
No. 0, the same one! 0. t, ≠ No. 71, same.

gos, 4Irt No., same J, jFF, JJ No. 4, same,
7/, No. 2.107, same, 730. '1.6, '2.7 JO, 1117, '3103+04L, '3. It can take various forms as described in prior patents such as TIIR, 2TO, and 4AO10031. Most commonly they consist of at least one pair of sheets containing separately an electron-donating colorless dye and an electron-accepting compound.

A method for manufacturing capsules is described in US Patent λ.

100, Q! t7, same, 2.100.4411 II
A method using coacervation of a hydrophilic colloid sol described by C, British Patent No. 1t7.727, same 10
．． Hiroshi 443, Dojiri, Ko6da, PL]/.

09/, 076, etc. or US Patent J/11) J≠04! - methods described in , etc.

In general, electron-donating colorless dyes are used singly or in combination with solvents (synthetic oils such as alkylated naphthalene, alkylated -/r-diphenyl, alkylated diphenylmethane, alkylated terphenyl, chlorinated paraffin, cotton oil, castor oil, etc.). By dissolving it in vegetable oil such as oil, animal oil, mineral oil, or a mixture thereof, incorporating it into microcapsules, and then applying it to a support such as paper, high-quality paper, plastic sheet, resin-coated paper, etc. Get a coloring agent sheet.

In addition, the electron-accepting compounds described below, alone or in combination, or together with other electron-accepting compounds, are dispersed in a binder such as styrene-butadiene latex or polyvinyl alcohol, and the pigments described below are used to produce paper, plastic sheets, and resin-coated paper. A developer sheet is obtained by coating a support such as the following.

The amounts of the electron-donating colorless dye and the electron-accepting compound to be used depend on the desired coating thickness, the form of the pressure-sensitive copying paper, the capsule manufacturing method, and other conditions, and may be appropriately selected depending on the conditions. It is easy for one skilled in the art to determine this amount to use.

When used in thermal paper, the electron-donating colorless dye and the electron-accepting compound have a particle size of 10 μm or less, preferably 3 μm or less, in the dispersion medium.
It is used after being crushed and dispersed to a particle size of μ or less. As a dispersion medium, generally 0. A water-soluble polymer aqueous solution with a concentration of about 1 to 10 cm is used, and dispersion is carried out using a ball mill, sand mill,
This is done using a horizontal sand mill, attritor, colloid mill, etc.

The ratio by weight of the electron-donating colorless dye and the electron-accepting compound used is preferably between 10 and 1, and particularly preferably between 1 and 3.
Nitrogen-containing organic compounds such as fatty acid amides, acetoacetanilide, diphenylamine, benzamide, carbazole, etc. Also F1a.

J-C m-) IJ Loubutan, 0-fluorobenzoyldurene, chlorobenzoylmesitylene, noon.

-Dimethylbiphenyl, or carboxylic acid esters such as dimethyl isophthalate, diphenyl phthalate, dimethyl terephthalate, methacryloxybiphenyl, etc., or polyether compounds such as di-m-
-Tolyloxyethane, β-phenoxyethoxyanisole, /-phenoxyethoxyethane, /-p-ethylphenoxyethane, bis-β-(p-methoxyphenoxy7)ethoxymethane, l-λ'-methylphenoxyco"-ether Phenoxyethane, l-tolyloxy-col-methylphenoxyethane, lI-co-diphenoxyethane,
/, 4A-diphenoxybutane, bis-β-(p-ethoxyphenoxy)ethyl ether, /-7 diphenoxy J
-p-chlorophenoxyethane, /-J'-methylphenoxy-λ-μ"-ethyloxyphenoxyethane, /-1'-methylphenoxycor≠"-fluorophenoxyethane, etc. are used together with a compound with a melting point of 7j0C-1300C It is preferable. These can be used in finely dispersed form at the same time as a colorless dye or at the same time as an electron-accepting compound.

In particular, it is preferable to disperse the colorless dye at the same time from the viewpoint of preventing fogging. These fecal doses are added at a weight ratio of 20% or more and 300% or less, especially ≠0% or more, relative to the electron-accepting compound. OqA or less is preferable.

- λ l - Additives are further added to the coating liquid thus obtained in order to meet various requirements.

As an example of additives, in order to prevent the recording head from becoming dirty during recording, oil-absorbing substances such as inorganic pigments and polyurea fillers are dispersed in the binder, and they also improve the releasability from the head. For this purpose, fatty acids, metal soaps, etc. are added. Therefore, in addition to colorless dyes and electron-accepting compounds that directly contribute to color development, additives such as pigments, waxes, antistatic agents, ultraviolet absorbers, antifoaming agents, conductive agents, fluorescent dyes, and surfactants are used. is applied onto the support to constitute the recording material.

Specifically, pigments such as kaolin, calcined kaolin, talc, waxite, diatomaceous earth, calcium carbonate, aluminum hydroxide, magnesium hydroxide, calcined gypsum, silica, magnesium carbonate, titanium oxide, alumina, barium carbonate, and sulfuric acid are used as pigments. Barium, mica, microballoon, urea-formalin filler, polyethylene chisel,
Particle size of cellulose filler is 0. /Naishi/! If you select one from μ, it will be fraudulent. Waxes include Nolough-in wax,
Examples include carboxy-modified chisel rough-in wax, cowna wax, microcrystalline wax, polyethylene wax, and higher fatty acid esters.

Metallic minerals include polyvalent metal salts of higher fatty acids, such as zinc stearate, aluminum stearate, calcium stearate, and zinc oleate.

These are dispersed and applied in a binder.

Water-soluble binders are generally used, such as polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, epichlorohydrin-modified polyamide, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, isobutylene-maleic anhydride. Examples include copolymers, polyacrylic acid, polyacrylic acid amide, methylol-modified polyacrylamide, starch derivatives, casein, and gelatin. In addition, water-resistant agents (gelling agents, cross-linking agents) are added to these binders for the purpose of imparting water resistance, and emulsions of hydrophobic polymers, specifically styrene-butadiene rubber latex, acrylic resin emulsions, etc. etc. can also be added.

Approximately 2 to 10 t7m2 of coating liquid is applied onto base paper, high-quality paper, synthetic paper, plastic sheet, or neutral paper.

Furthermore, the resistance can be improved by providing a protective layer of about 00λ to λμ consisting of a water-soluble or water-dispersible polymer compound such as polyvinyl alcohol, hydroxyethyl starch, or epoxy-modified polyacrylamide and a crosslinking agent on the coated surface layer. .

When used for thermal paper, OLS, 2.221rj
No. t1, same, 2/101144, Special Publication No. 3.2-207
Various aspects described in ≠λ etc. can be taken. Alternatively, operations such as preheating, humidity control, or stretching of coated paper may be added prior to recording.

For example, the electrically conductive thermal paper is disclosed in Japanese Patent Application Laid-open No. 2-//34L and t.
o-4! Manufactured by the method described in No. 30, etc. Generally, a coating liquid in which a conductive substance, a basic dye mainly composed of the fluoran derivative of the present invention, and an electron-accepting compound are dispersed together with a binder is applied to a support such as paper, or
The electrically conductive thermal paper of the present invention is produced by coating a conductive material on a support to form a conductive layer, and then coating the 71c coating solution with a colorless dye, an electron-accepting material, and a binder dispersed thereon. Incidentally, the sensitivity can also be improved by using all of the thermofusible substances mentioned above in combination.

The photosensitive and pressure sensitive paper is manufactured, for example, by the method described in Japanese Patent Application Laid-Open No. 17-1989 (IJt). Generally silver iodobromide, silver bromide, silver behenate, Michler's ketone, benzoin derivatives,
A photopolymerization initiator such as a benzophenone derivative and a crosslinking agent such as a polyfunctional monomer such as polyallylated compound, poly(meth)acrylate', or poly(meth)acrylamide are used together with a colorless dye and optionally a solvent to form a synthetic resin wall such as polyether urethane or polyurea. is encapsulated in a capsule. After imagewise exposure, the colorless dye in the unexposed area is brought into contact with a color developer and colored.

The electron-accepting compound according to the present invention is synthesized by a known method. For example, it can be obtained by aryloxyalkylation of the corresponding hydroxysalicylic acid derivative.

<Examples of the Invention> Examples will be shown below, but the present invention is not limited only to these examples.

Example 1 (1) Preparation of color former sheet A color former was dissolved in 30t of λ-anilino-3-methyl-6-diethylaminofluorane/91 alkylated naphthalene, which is an electron-donating colorless dye. This solution was added to a water sot in which gelatin 6f and gum arabic≠tf had been dissolved, with vigorous stirring, and emulsified to form oil droplets with a diameter of lμ to 10μ, and then 2t of water was added. Acetic acid was added little by little to bring the pH to about ≠ to cause coacervation, creating a wall of gelatin and gum arabic around the oil droplets, and formalin was added and the pH was raised to 9 to harden the wall.

The microcapsule dispersion thus obtained is applied to paper and dried to obtain a color former sheet.

■ Preparation of color developer sheet Zinc l-β-phenoxyethyloxysalicylate 209, which is an electron-accepting compound, is well dispersed in an aqueous solution of jt4de rivinyl alcohol with an aqueous pressure of 001, and further kaolin (Jossia kaolin>sot) is added. A coating solution was obtained.The obtained coating solution was applied to paper and dried to obtain a color developer sheet.

When the thus prepared color former sheet and color developer sheet were brought into contact with each other and pressure or impact was applied, a black printed image was instantaneously obtained. This image had high density and excellent light resistance and heat resistance.

Example λ In the electron-accepting compound of the developer sheet of Example 1,
3. ! -Zinc bis(α-methylbenzyl)salicylate l
A color developer sheet was obtained in the same manner as in Example 1 using 10f of zinc O1 and μmβ-p-)lyloxyethoxysalicylate. When color was developed in the same manner as in Example 1, a black printed image was obtained. This material was highly concentrated and had excellent light resistance and heat resistance.

Examples 3 to 10 Electron-donating colorless dye, electron-accepting compound, thermofusible substance dispersion shown in Table 1 OTF: Dispersed in a ball mill overnight with 100 ml of TL polyvinyl alcohol (Kuraray PVA10) aqueous solution to reduce the volume. The average particle size was 3μ.

On the other hand, calcined kaolin (Anisilex-93) 109 was dispersed with a homogenizer together with 1 tot of a 0.1% solution of sodium hexametaphosphate.

Each dispersion liquid is dispersed as described above, and the electron-donating colorless dye dispersion jf, the electron-accepting compound dispersion lθt, and the thermofusible substance dispersion 7? , calcined kaolin dispersion JJt, and then an emulsion of zinc stearate ttt and an aqueous solution of sodium (coethylhexyl)sulfosuccinate of 24! A coating liquid was obtained by adding t. This coating liquid was dried on high-quality paper with a basis weight of 109/fi2, and the coating amount was At/m2.
The coated paper was coated with a wire parr so that

Comparative Example/-1 A coated paper was obtained in the same manner as in Example 3 except that the electron-accepting compound in Example 3 was replaced with the compound shown in Table 2.

-λ Tar- Color density is Fujitsu High-speed facsimile IJFF-2000
Using a copy of the Image Electronics Engineers of Japan Test Chart 3, the color density was measured using a Macbeth RD-ta/I type densitometer. On the other hand, chemical resistance was evaluated by impregnating door paper with ethanol and castor oil and superimposing it on the colored surface of the recording paper obtained by the above method, and evaluating the degree of fogging in the white area and decolorization (discoloration and fading) in the colored area. did.

Table 3: ◎ Very good O Excellent (slight changes observed) Δ Practical use (images can be read) It can be seen that the sensitivity is high, and there is no capri color development or decolorization of the colored area due to chemicals, and it has extremely excellent friend performance.

Patent applicant: Fuji Photo Film Co., Ltd. -3≠-

Claims (1)

[Claims] A recording material containing an electron-donating colorless dye and an electron-accepting compound, the recording material comprising a salicylic acid derivative having an aryloxyalkyloxy group as a substituent or a metal salt thereof as the electron-accepting compound.